Fungicide compositions

ABSTRACT

This invention provides a novel fungicide composition which has a bicarbonate-containing inorganic salt ingredient which enhances the efficacy of a fungicide ingredient for the treatment of cultivated crops. An invention fungicide composition also contains a surfactant ingredient, and a water-soluble organic compound which functions as a compatibility enhancing ingredient in aqueous formulations, and the ingredients improve the spreadability and adhesiveness of the composition when applied to foliage. An invention fungicide composition also contains a fertilizer-effective ratio of nitrogen, phosphorus and potassium.

This application is a division, of application Ser. No. 07/883,422,filed May 12, 1992 now abandoned.

BACKGROUND OF THE INVENTION

Fungi are plants which obtain their nutrition from an organic carbonsource. The body of the fungus secretes enzymes which degrade theorganic substrate on which they are growing and yield smaller entities.These in turn are absorbed into the body of the fungus and aremetabolized and provide energy to carry on vital processes.

The control of phytopathogenic fungi is of great economic importancesince fungal growth on plants or on parts of plants inhibits productionof foliage, fruit or seed, and the overall quality of a cultivated crop.

There is also a serious worldwide problem of mold growth in foodmaterials, such as grains, animal feeds, animal feed ingredients, wholecrop, and hay. This problem is most serious in tropical zones of boththe eastern and western hemispheres, where sustained high humiditiescause excessive moisture to be absorbed in such products.

One reason molds present such a serious problem is that they producedangerous mycotoxins, some of which are carcinogenic. One of the commonmolds Aspergillus flavus, produces the mycotoxin aflatoxin which, inaddition to other toxic characteristics, interferes with the immunesystem's ability to produce gamma globulin, the protein that is part ofthe immune system. The resulting breakdown of the immune system rendersanimals that have ingested such mold vulnerable to a variety ofdiseases.

Because of the vast economic ramifications of fungal propagation inagricultural and horticultural cultivations, a broad spectrum offungicidal and fungistatic products have been developed for general andspecific applications.

Of particular interest with respect to the present invention embodimentsare fungicide compositions which contain one or more inorganicbicarbonate compounds. It is known that bicarbonate and carbonatecompounds exhibit fungicidal properties for agricultural purposes.

Phytopathology, 48, 169 (1931) by R. H. Marloth describes studiesinvolving the physiology of fungi. The reference reports studies whichdemonstrate that sodium and potassium bicarbonate and carbonate saltsare toxic to fungi such as Penicillum italicum and Penicillum digitalum.

U.S. Pat. No. 1,560,558 discloses the use of one or more of lithiumcarbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate,potassium carbonate and ammonium bicarbonate as a fungicide.

Japanese patent 53090319 describes the application of potassiumbicarbonate as an active biocide for the control of fungal diseasescommon to tomato and cucumber plants.

Japanese patent 53118523 describes the combination of sodium bicarbonateand lecithin as an active agent for the control of agricultural andfruit storage fungus diseases.

Japanese patent 56043207 describes a biocidal composition containingsodium bicarbonate and a polyglycerol fatty acid ester. The biocidecontrols Penicillum digitatum on oranges, Sphaerotheca fuligenea oncucumbers, Piricularia oryzae on rice, and mosaic virus on tomatoes.

Japanese patent 60097909 describes a soil fungicide prepared by admixingslaked lime with sodium bicarbonate, potassium bicarbonate, boric acidand phenolphthalein.

German patent DE 2927994 describes a fungicide which consists of sodiumbicarbonate incorporated into a food-compatible surfactant such assaccharose laurate.

Japanese patent 57062208 describes horticultural fungicides in which theaddition of sodium bicarbonate to polyoxin or thiophanatemethylincreases the fungicidal activity of the organic biocide againstBotrytis cinerea on cucumbers.

Japanese patent 58023609 describes an agricultural fungicide composed ofa mixture of sodium bicarbonate or potassium bicarbonate with cuprichydroxide, basic copper carbonate or basic copper sulfate. Thecombination of ingredients exhibits a synergistic fungicidal effectagainst cucumber early blight, tomato wilt, rice sheath blight, riceblast and citrus canker.

There remains a continuing need for the development of new and moreeffective fungicides which possess preventive, curative and systemicactivity for the protection of cultivated plants, with a minimum ofphytotoxic side effects.

Accordingly, it is an object of this invention to provide a biocidecomposition which is a blend of inorganic and organic compoundsexhibiting fungicidal properties.

It is another object of this invention to provide a fungicidecomposition which is a dry blend of ingredients which include abicarbonate salt which enhances the biocidal activity of a fungicideingredient.

Other objects and advantages of the present invention shall becomeapparent from the accompanying description and examples.

DESCRIPTION OF THE INVENTION

One or more objects of the present invention are accomplished by theprovision of a fungicide composition which is a dry blend formulationcomprising (1) an ingredient selected from alkali metal and ammoniumbicarbonates; (2) a compatibility enhancing ingredient selected fromwater-soluble organic compounds which are in solid form at a temperaturebelow about 10° C.; and (3) a fungicide ingredient.

In another embodiment this invention provides an aqueous fungicidalformulation having a content comprising (1) an ingredient selected fromalkali metal and ammonium bicarbonates; (2) a compatibility enhancingingredient selected from water-soluble organic compounds which are insolid form at a temperature below about 10° C.; and (3) a fungicideingredient.

The inorganic salt ingredient is selected from compounds which includesodium bicarbonate, potassium bicarbonate, lithium bicarbonate andammonium bicarbonate. In a further embodiment, the inorganic saltingredient can include an additional compound selected from sodiumcarbonate, potassium carbonate, lithium carbonate and ammoniumcarbonate.

The inorganic salt ingredient typically will comprise between about10-80 weight percent, based on the weight of dry blend formulation.

Illustrative of inorganic salt ingredients in a formulation are sodium,potassium, lithium or ammonium bicarbonate, or mixtures such as sodiumbicarbonate and potassium bicarbonate; sodium bicarbonate and ammoniumbicarbonate; potassium bicarbonate and ammonium bicarbonate; sodiumbicarbonate, potassium bicarbonate and ammonium bicarbonate; sodiumbicarbonate and potassium carbonate; potassium bicarbonate and potassiumcarbonate; and the like.

Multiple inorganic salt compounds can be utilized in a broad range ofmolar quantities relative to each other. The molar quantity of acarbonate salt compound normally is determined by pH controlconsiderations when aqueous formulations are prepared. The content of acarbonate salt compound can be varied to control the pH at a desiredlevel in the range of 7.5-12. Aqueous fungicidal formulations of thepresent invention tend to have a higher fungicidal activity at higher pHvalues.

A compatibility enhancing ingredient of the present invention fungicidecompositions is a water-soluble organic compound which is in solid format a temperature below about 10° C. Suitable compounds includeacetamide, acetylurea, alanine, aminoquanidine, aminomalonate salt,aminopyridine, arabinose, benzenesulfonate salt, benzoate salt,citraconate salt, citrate salt, crotonate salt, cyclohexanol,dihydroxyacetone, dihydroxyacetone phosphate salt, dihydroxybenzene,dimethylurea, ethanolamine, ethyl alaninate, ethyl arsonate,ethylglycine, ethylurea, ethylenedisulfonate salt, ethyleneurea,paraformaldehyde, fucose, glutamate salt, glycerol, glycerol nitrate,glycerol phosphate guanidine, hexamine, mannitol, fructose, glucose,hydroxyurea, lactate salt, lactose, lysine, maleic amide, malonate salt,maltose, maltodextrin, methoxypyridine, methyl acetate, methylcarbamate, methyl ethyl sulfone, methyl glucoside, methylhydantoin,methylinositol, methylthiourea, methyluracil, methylurea,methylenedisulfonate salt, muconate salt, naphtholdisulfonate salt,nitrobenzoate salt, nitropentanediol, nitrophenol salt, nitrourethane,pentaglycerol, phenol, phenylenediamine, polydextrose, propionamide,propyl carbamate, propylurea, purine, pyrazine, pyrimidine, ribose,saccharate salt, sarcosinate salt, semicarbazide, sorbate salt,succinimide, sucrose, tartarate salt, tetrahydrobenzoate salt,tetrahydroquinoline, tetrazine, thiourea, threonine, triaminobenzene,triazole, triethylphosphine oxide, triethylenetetramine,trihydroxybenzene, trimethylurea, urea, xylenol, xylose, xylyleneglycol, polyvinylpyrrolidone, sodium carboxymethylcellulose, xanthangum, guar gum, locust bean gum, gum acacia, gum tragacanth, potassiumalginate, potato agar, and the like.

The compatibility enhancing ingredient is incorporated in a quantitybetween about 0.5-20 weight percent, based on the weight of ingredientsin a dry blend fungicide composition.

The term "water-soluble" as employed herein refers to a compatibilityenhancing organic compound which has a solubility of at least about onegram per 100 grams of water at 25° C.

The fungicidal ingredient of an invention fungicide composition isincluded in a quantity which will provide a concentration between about0.01-10 weight percent of the medium which is being applied to seeds,plants, trees, harvested crops, soil, and the like. The medium can be adry blend dusting powder or an aqueous spraying formulation.

The fungicidal ingredient can be selected from a wide variety of organicand inorganic compounds or mixtures which are known and used inagriculture and horticulture applications, such as those listed inAgricultural Chemicals, Book IV, Fungicides, 1989 Revision (W. T.Thomson, Thomson Publications, Fresno, California 93791).

The general categories of fungicidal-active compounds include anilides,dithiocarbamates, halogenated derivatives, heterocyclic nitrogenderivatives, metallic derivatives, and the like.

Illustrative of fungicidal compounds are carbendazim, benomyl,thiophanate-methyl, thiabendazole, fuberidazole, dichlofluanid,cymoxanil, oxadixyl, metalaxyl, furalaxyl, benalaxyl, fenarimol,iprodione, procymidone, vinclozolin, penconazole, myclobutanil,pyrazophos, ethirimol, ditalimfos, tridermorph, triforine, nuarimol,triazbutyl, guazatine, propiconazole, prochloraz, flutriafol,chlortriafol, triadimefon, triadimenol, dichlobutrazol, fenpropimorph,fenpropidin, chlorozolinate, fenfuram, carboxin, oxycarboxin,methfuroxam, dodemorph, blasticidin S, kasugamycin, edifenphos, kitazinP, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole,pyroquilan, chlorbenzthiazone, neoasozin, polyoxin D, validamycin A,repronil, flutolanil, pencycuron, diclomezine, phenazin oxide, nickeldimethyldithiocarbamate, techlofthalam, bupirimate, etaconazole,cypofuram, biloxazol,dimethirimol, fenapanil, pyroxyfur, polyram, maneb,mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet,zineb, propineb, binapactryl, nitrothalisopropyl, dodine, dithianon,fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran,copper oxychloride, copper sulphate, Bordeaux mixture, and the like.

An invention fungicide composition can be applied directly to thefoliage of plants, bushes and trees, or to the soil of a cultivatedfield, or to seeds prior to planting, or to paddy water and hydroponicculture systems. The fungicidal methods include preventive, protective,prophylactic and eradicant treatments.

Invention fungicide compositions can be in the form of dusting powdersor granules, which optionally can include a solid diluent such asbentonite, calcium carbonate, magnesia, gypsum, kieselguhr, diatomaceousearth, and the like. Granules can be formed by impregnating pellets offiller with the fungicide composition ingredients, or by pelleting a dryblend fungicide composition in admixture with a powdered filler.

An invention fungicide composition also can be in the form of adispersible powder in combination with a surfactant to facilitatedispersion of the powder in an aqueous medium. The surfactant isincorporated in a fungicide composition in a quantity between about 1-20weight percent, based on the weight of water-insoluble ingredients.

The surfactant can be a cationic, anionic or nonionic type, or a mixturethereof. Suitable surfactants include cetyltrimethylammonium bromide;sodium lauryl sulfate; sodium dodecylbenzene-sulfonate; ammoniumlignosulfonate; condensation products of ethylene oxide with fattyalcohols, amines or alkylphenols; partial esters of fatty acids andhexitol anhydrides; and the like.

An invention fungicide composition can be in the form of aqueousdispersions for use as dips, or as sprays for use in electrodynamicspraying techniques.

The ingredients in an invention fungicide composition can be selected toinclude nitrogen, phosphorus and potassium elements, in a ratio thatallows the composition to function as a fertilizer in addition to itsfunction as a fungicide, when applied to cultivated crops.

An invention fungicide composition can include one or more otherbiologically active ingredients, such as those which exhibit herbicidal,insecticidal or plant growth regulating activity.

A fungicide composition of the present invention has a novel combinationof properties for the practice of pesticide control in agricultural andhorticultural application.

The inorganic salt ingredient exhibits fungicidal properties, and theefficacy of the main fungicide ingredient is enhanced by the presence ofthe inorganic salt ingredient. A lesser quantity of fungicide ingredientthen can be employed to achieve a desired degree of fungus control.

A present invention fungicide composition can be formulated to exhibitlittle or no phytotoxicity, or to minimize the toxic effects of saltstress on plants by the inorganic salt ingredient.

A significant feature of a present invention fungicide composition isthe inclusion of a compatibility enhancing agent as an essentialingredient. Migration and settling of solid ingredients is minimized,and a dry blend formulation has a more uniformly distributed contentbecause of the presence of the compatibility enhancing ingredient. Anaqueous fungicide formulation has exceptional long term stability,without phase separation and precipitation of solids.

As a further advantage, a present invention aqueous fungicidalformulation has improved spreadability and adhesiveness when applied toplant foliage, and resists post-application fungicide drift. An appliedformulation also exhibits humectant properties on coated foliage, andincreased fungicidal efficacy because of the presence of thecompatibility enhancing ingredient.

The following examples are further illustrative of the presentinvention. The components and specific ingredients are presented asbeing typical, and various modifications can be derived in view of theforegoing disclosure within the scope of the invention.

EXAMPLE I

This Example illustrates the preparation of a fungicide dusting powderin accordance with the present invention.

A blend of the following ingredients is prepared:

    ______________________________________                   Parts    ______________________________________    KHCO.sub.3       30    triphenyltin acetate                      5    mannitol          5    talc             65    ______________________________________

The formulated blend is milled to provide a powder with a particle sizeof less than 0.5 micron.

EXAMPLE II

This Example illustrates the preparation of a copper-containingagricultural fungicide composition.

A blend of the following ingredients is prepared as a wettable powderformulation:

    ______________________________________                    Parts    ______________________________________    NaHCO.sub.3       30    basic copper sulfate                      5    dihydroxybenzene  2    sodium lignosulfonate                      2    kaolin            30    ______________________________________

The formulation is suspended in water (20% by weight solids), and isapplied to plant foliage.

A synergistic fungicidal effect is observed when the aqueous formulationis applied to control cucumber damping-off, cucumber early blight,tomato wilt, and rice blast.

The formulation is applicable to seeds, soil and foliage.

Similar fungicidal activity is observed when an aqueous solution (10% byweight solids) containing dissolved NH₄ HCO₃ (60 parts), K₂ Co₃ (35parts), basic copper sulfate (5 parts) and sodium benzenesulfonate (5parts) is applied to plant foliage.

EXAMPLE III

This Example illustrates the preparation of a granulated fungicidecomposition which has a high suspension capacity in water.

A mixture of the following ingredients is prepared:

    ______________________________________                    Parts    ______________________________________    Chloridazon       60    NH.sub.4 HCO.sub.3                      10    KHCO.sub.3         5    hexamine           2    sodium lignosulfonate                      20    ______________________________________

The mixture is dispersed in water, and spray-dried at 180° C. Theresulting granules have a 70% suspension capacity in water.

EXAMPLE IV

This Example illustrates the preparation of fungicide compositiontablets which rapidly disintegrate and disperse in water.

    ______________________________________                    Parts    ______________________________________    Captan            40    NaHCO.sub.3       35    citric acid       12    Lomar PWA 10.sup.(1)                      10    glyoxal            2    sodium lignosulfonate                       1    ______________________________________     .sup.(1) sodium salt of alkylarylsulfonate condensation product (Jacques     Wolf & Co.)

The ingredients are blended, and formed into tablets which disintegrateand disperse in water within about five minutes at 25° C.

EXAMPLE V

This Example illustrates the preparation of a water-dilutable liquidconcentrate fungicide composition.

A liquid concentrate is prepared from the following ingredients:

    ______________________________________                     Parts    ______________________________________    Carboxin           10    NaHCO.sub.3 (300 mesh)                       35    KHCO.sub.3 (300 mesh)                       35    oleic acid monoglyceride                       30    glyceryl monooctanoate                       10    glycerol            5    ______________________________________

The ingredients are admixed and heated at 40° C. to form a concentratedliquid suspension. When the suspension is diluted with water, it forms astable emulsion which has utility as a fungicide spray in agriculturalapplications.

EXAMPLE VI

This Example illustrates the preparation of an aqueous fungicidalformulation stabilized with a nonionic surfactant phosphate ester salt.

    ______________________________________                   Parts    ______________________________________    Benomyl          22    KHCO.sub.3       10    NH.sub.4 CO.sub.3                     10    polyoxyethylene   5    (7.6 mol)-    phenylphenol ether    phosphate diethanol-    amine salt    sucrose           5    water            50    ______________________________________

The ingredients are added to the water medium with stirring to form astable emulsion.

EXAMPLE VII

This Example illustrates the preparation of a fungicide compositionsuitable for treatment of seeds.

A fungicide composition is prepared by mixing and grinding the followingingredients:

    ______________________________________                     Parts    ______________________________________    pentachloronitrobenzene                       10    sodium nitrophenol  5    NH.sub.4 HCO.sub.3 20    K.sub.2 CO.sub.3   20    mineral oil        10    china clay         40    ______________________________________

EXAMPLE VIII

This Example illustrates the preparation of a fungicide-fertilizercomposition.

A blend of the following ingredients is prepared:

    ______________________________________                   Parts    ______________________________________    melamine         40    urea             30    potassium glycerol                     20    phosphate    Carboxin          5    KHCO.sub.3       15    ______________________________________

Granules are prepared by tumbling the blend, spraying added water toform tacky solids, and then drying the granulated product.

What is claimed is:
 1. A fungicide composition which is a dry blendformulation comprising (1) between about 10-80 weight percent of aningredient selected from the group consisting of alkali metal andammonium bicarbonates, (2) between about 0.5-20 weight percent of acompatibility enhancing ingredient selected from the group consisting ofwater-soluble polyhydroxy compounds which are in solid form at atemperature below about 10° C., (3) between about 0.01-10 weight percentof a fungicide ingredient, and (4) between about 1-20 weight percent ofa surfactant ingredient, based on the weight of water-insolubleingredients; wherein the composition contains nitrogen, phosphorus andpotassium elements in a ratio which is functional as a fertilizerformulation.
 2. A fungicidal composition in accordance with claim 1wherein the content of inorganic salt ingredient comprises potassiumbicarbonate.
 3. A fungicide composition in accordance with claim 1wherein the content of inorganic salt ingredient comprises ammoniumbicarbonate.
 4. A fungicide composition in accordance with claim 1wherein the content of inorganic salt ingredient comprises potassiumbicarbonate and ammonium bicarbonate.